Method of separatng calcium and magnesium chlorides



Oct. 28, 1930. A. K. SMITH ET AL METHOD OF SEPARATING CALCM-AND MAGNESIUM CHLORIDES Filed June le, 1925 i' and magnesium chlorides,

Patented Oct. 28, 193

, UNITED STATES PATENT 4ol-rlcit y BERTKELVIN SMITH, OF MIDLAND, MICHIGAN, AND CARL F. kIER'UT'ION, 0F EAST CLEVELAND, OHIO, ASSIGNORS T0 THE CHEMICAL COMPANY, OF MIDLAND,

MICHIGAN, A CORPORATION OF MICHIGAN s METHOD 0F SEPARATNG CALCIUM AND MAGNESIUM CHLORIDES Original application led'SeptembervZS, 1923, Serial No. 665,737. :Divided` and this application led .Tune

16, 1925. Serial No. 37,465.

'In our `co-pending application, iiled September 29, 1,923, Serial No. 665,737, there is disclosed an improved method or process for treatingbrines .which contain calcium with the object of separating the chlorides from each other. Incidentally to such process, the calcium and magnesium chlorides, at least in part, are crystallized out of the solution in the form of a double salt known as tachydrite (oaoreMgonim),

which with adherent mother liquorV would contain approximately25 per cent calcium chloride and 32 per cent magnesium chloride. These crystals are mother liquor and, by appropriate treatment,

the calcium chloride content may be sepaprocess. v

It will be understood of course that 'the method of separation involved is not limited in its utilization to a mother liquor derived in the specific manner just set forth but that such treatment 4may be employed for the separation of magnesium and calcium chlorides occurring in 'any' similar solution, or mixture, however derived.`

To the accomplishment of the foregoing and related ends, the invention then consists of the steps fully described and particularly pointed out in the claims, the annexed draw- .ingV and the following description setting forth in detail one improved method of carrying out the invention; such disclosed mode, however, illustrates merely the various ways tion at temperatures between 90 then separated from the.v

chloride from the g in which the principle of the invention may be used.

In said annexed drawing The single igure is a diagram wherein the saturation points ofycertain compounds involved in the process are shown by appropriate curves.

When an aqueous solut-ion'of calcium chloride and magnesium chloride, in which the molecular proportion of calcium chloride to magnesium chloride is greater than two to is suiiiciently concentrated by evapora- C. and

175 C. (the lower limit depending upon the proportion) a hydrated double chloride having the composition MgCl2.2 CaCl2.6I-I2O is precipitated. As the evaporation is continued, (the temperature being held constant) and more of the double chloride is one,

- formed, the molecular proportion of calcium chloride to magnesium chloride in the remaining solution continually increases until calcium chloride dihydrate, CaCl2.2H2O, be-

ins to precipitate along with the double chloride.l Fromthis point on, further evaporation does .notf change the composition of the remaining solution; and for a given temperature the solution thus obtained (i. e. the mother liquor) contains the minimum amount of magnesium chloride. The relation between the composition of the final solution and the temperature is shown by the attached diagram. It will be seen that, as the temperature is increased, the magnesiumchloride content decreases, approaching onehalf of one per cent at 175 C.; on the other hand, the calcium chloride content increases, approaching that of a saturated solution ofv calcium chloride alone (i. e. of 'calcium chloride containing no magnesium chloride) To purify calcium chloride `containing magnesium chloride in an amount less thari'is equivalent to a molecular proportion of two to one, it is therefore necessary only to concentrate a solution of the impure material and-"remove the crystals formed at a temnesium chloride is obtained by carrying out the separation of crystals from solution at .the maximum temperature, the water content of the mixture having been reduced until the crystals consist of the hydrated double chloride,

MgCl2.2CaCl2.6I-I2O, and a smaller amount of calcium chloride dihydrate, CaCl22H2O.

The presence of calcium chloride dihydrate in the crystals, however, ,is' a disadvantage during separa-tion for two reasons: the dificulty of separation is increased, and the ef-v ficiency of the process is reduced because of the increased calcium chloride content of the crystals. It is, therefore, usually preferable .to remove slightly less water than will cause ing the crystals, or the evaporation maybe carried out under sufficient vacuum to reduce the boiling point of the final solution to the proper temperature for filtration. In

-either case, the crystals may be removed as soon as formed, or left in until the precipitation is complete before separating from the mother liquor.

A still different procedure may be adopted to insure a minimum amount of magnesium chloride left in solution, together with a minimum amount of calcium chloride in the crystals, as follows:

The boiling point during evaporation is reduced by vacuum to a temperature (e. g. 120 C.) below that at which the separation of crystals is `to be made. Evaporation is continued until CaCl2-2H2O begins to precipitate with the crystals. The mixture is then heated, during agitation, untily the CaCl2-2H2O is just ,dissolved (say 14010 C.) and theremaining' crystals (consisting of MgCl,.2CaCl2.6I-I2O alone) separated from the motherliquor at that temperature.

The principle involved in the process is simply the control of the total amount of water (as H2O) in the mixture of crystals and mother liquor before removal of the crystals. This percentage of total Wat-er in the mixture depends upon `the propor-tion of calcium chloride to magnesium chloride (conveniently expressed as per cent MgCl2 in the total anhydrous chlorides) and upon the temperature of removal of crystals; while the composition of the mother liquor depends only upon the tempera-ture, as hereinbefore explained.

Itl isgapparent tha-t if the raw material already contains less than the required amount of water, instead of evaporating, it will benecessary only to add water and heat as required, agitate until crystals and solution are in equilibrium, and then remove the crystals. v

vThe apparatus employed may consist of the usual vacuum evaporator (or open pan in thel case of evaporation at atmospheric pressure), a tank equipped with agitator and coils for heating or cooling, and a filtering device,` e. g., box filter, false-bottomed tank,

filter press, or centrifuge.

The crystals of hydrated magneslum calcium chloride,

are obtained as a by-product. These are contaminated with'more or less mother liquor, and perhaps'also with calcium chloride dihydrate (CaCl22H2O). However, the molecular ratio of calcium chloride to magnesium chloride should be only `slightly more than two to one. Since this by-product is extremely hygroscopic, it may be put on the marketA directly as a dust-preventive. It is probably more advantageously disposed of by treating according to the method of our co-pending application, Serial No. 665,737.

'If used in this way, it'should be admitted to that process with the brine which has been stated.

Other modes of applying the rinciple of ourv invention may be employe instead of the one explained, vchange eing made as regards the process herein disclosed, provided the step or steps stated by any of the following claims or the equivalent of such stated step or steps be employed.

We therefore particularly point out and distinctly claim as our invention :l-

1. In a method of treating a brine of the character described, the steps which consist in evaporating such brine to crystallize out the sodium chlqrideevaporating the residual brine containing calcium and magnesium chlorides to crystallize out the latter in the form of tachydrite and leave a. mother liquor having a higher proportion of calcium chloride to magnesium chloride than the original brine, and removing the ma nesium chloride from such mother liquor as t e hydrated doublechloride.

MgCl22CaCl26-H2O which theby-product may be returned as 105 2. In a method of separating calcium chloride from magnesium chloride in solution to gether, the steps which consist in evaporating such solution to crystallize out the latter in the form of tachydrite and leave a mother liquid having a higher proportion of calcium chloride to magnesium chloride than the original solution, and removing the magnesium chloride from such mother liquor by concentrating such liquor and removing the crystals formed at a temperature between 90o and 175o C.

3. In a method of l'separating calcium chloride from magnesium chloride in solution together, the steps which consist in evaporating such solution-to crystallize out the latter in the form of tachydrite and leave a mother liquor having a higher proportion of calcium chloride to magnesium chloride than the original solution, and removing the magnesium chloride from such mother liquor by concentrating such liquor and removing the crystals formed at a temperature between 90 and 175o C., the Water content being reduced until the crystals thus formed consist principally of the hydrated double chloride,

Mgo122cac12-en2o.

4. A method of purifying calcium chloride containing magnesium chloride in an amount less than is equivalent to a molecularproportion of two to one, which comprises concentrating a solution of such 'chlorides and removing the crystals formed at a temperature between 90 and 17 5 C.

' 5. A method rof purifying calcium chloride containing magnesium chloride in an amount less than is equivalent to a molecular proportion of two to one, which comprises concentrating a solution of such chlorides and removing the crystals formed at a temperaturebetween 90 and 175 C., the Watercontent of the solution being reduced until the crystals thus formed consist principally of the hydrated double chloride,

MgCl2.2CaCl2.6H2O.

and removing the crystals formed thereby.'

7. A method of purifying calcium`v chloride containing magnesium chloride in amount less than is equivalent to a molecular proportion of 2 to 1, which consists in removing magnesium chloride by crystallization as the double chloride,

I 8. A method of purifying a solution of calcium chloride containing magnesium chloride in amount less than is equivalent to a molecular proportion of 2 to l, which consists in concentrating such solution at a temperature and presssure whereat the hydrated double chloride,

Mgcigccacnemo,

crystallizes out, While avoiding substantial crystallization of calcium chloride dihydrate.

9. A method of purifying calcium chloride containing magnesium chloride in amount less than is equivalent to a molecular 'proportion of 2 to 1, which comprises con- Mgoigecaciznzo,

from the mother liquor.

Signed by me this fth day of J une, 1925.

ALBERT KELVIN SMITH.

Signed by me this tenth day of June, 1925.

CARL F. PRUTTON.

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